本研究以複合式陰離子聚合與硫醇-己內醯胺活性自由基聚合(Mercaptan/ε-caprolactam living polymerization)系統製備功能性團鏈共聚物，並將其應用於聚乳酸物性的改善。研究結果顯示，經由複合式陰離子聚合與硫醇-己內醯胺活性自由基聚合系統可成功製備聚苯乙烯(PS)-甲基丙烯酸甲酯(PMMA)雙嵌式團鏈共聚物(SM)，利用0.5 wt%的SM與聚乳酸進行熔融摻混，可有效提升聚乳酸的結晶速率，半結晶時間(t1/2)最小可為2.4 mins (純聚乳酸為 9.6 mins)，相對結晶度最高可為58 % (純聚乳酸為 37 %)；由偏光顯微鏡(POM)觀察結果可知，SM的添加有效提升晶核的密度，使聚乳酸的結晶較為小與緻密。此外，當PS鏈段與PMMA鏈段以雙嵌式團鏈共聚物型式同時存在於聚乳酸中時，相較於PS或PMMA單獨存在於聚乳酸，SM雙嵌式團鏈共聚物對於聚乳酸結晶性的提升具有增效作用(Synergy effect)；其中，SM雙嵌式團鏈共聚物中的PS鏈段與聚乳酸不相容，因此提供了誘導異相晶核生成的位置，PMMA鏈段則有助於SM雙嵌式團鏈共聚物於聚乳酸中的分散性。
改變雙嵌式團鏈共聚物SM中PS與PMMA鏈段分子量的比例，評估其對聚乳酸結晶特性的影響，研究結果顯示當PMMA分子鏈段太長時，會阻礙聚乳酸結晶運動，導致結晶速率下降。對於SM雙嵌式團鏈共聚物而言，當PMMA鏈段與PS鏈段分子量比例為4時，在促進聚乳酸的結晶速度應用上可得到最佳化值。此外，本研究亦利用苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)與聚乳酸進行混摻，探討SBS摻混比例對於聚乳酸結晶行為與物性所造成的影響，研究結果顯示SBS可有效改善聚乳酸的結晶特性，以適當比例的SBS與聚乳酸進行混摻，可得到一具有機械強度與延伸性的生質合膠，當SBS的混摻比例為50 wt%時，相較於純聚乳酸，延伸率可提升2.5倍，抗衝擊強度可提升1.5倍。
另一方面，同樣利用複合式陰離子聚合與硫醇-己內醯胺自由基活性聚合系統製備聚丁二烯-甲基丙烯酸甲酯雙嵌式團鏈共聚物(PBM)，並將其應用於聚乳酸與高密度聚乙烯(HDPE)的熔融摻混改質。研究結果顯示，將聚乳酸與聚乙烯及上述的雙嵌式團鏈共聚物PBM以20/80/3的重量比例進行熔融摻混，PBM能有效提升摻混體的延伸率與耐衝擊特性，延伸率提升約4倍，耐衝擊性提升約1.5倍，其混摻分散的微分散相粒徑可小於 0.5 μm。因此，PBM可有效作為聚乳酸與聚乙烯兩不相容材料的相容助劑。此一複合式活性聚合法可用於合成功能性團鏈共聚物，將可進一步拓展功能性團鏈共聚物的應用，同時提升其商業化的可能性。所開發聚乳酸改質材料，其結晶速率、延伸率與抗衝擊強度得到明顯的改善，將有助於此生質材料的應用推廣。

In this study, a series of block copolymers were prepared combining anionic polymerization and mercaptan/ε-caprolactam living polymerization. To evaluate how the polystyrene-block-poly(methyl methacrylate)(SM) copolymer affected the crystallization behavior of PLA, 0.5 wt% SM was melted blended with PLA. The results showed that SM effectively increased the crystallization kinetics of the PLA. To investigate the influence of the asymmetric ratio of SM on the crystallization rate of PLA, we synthesized SM featuring distinct asymmetric ratios and subsequently melt-blended the polymers with PLA. The results indicated that adding 0.5 wt% SM increased the crystallization rate of PLA when the value of the asymmetric ratio of SM was  4. In addition, poly(styrene-butadiene-styrene) copolymer was also used to enhance the crystallization ability and mechanical properties of PLA. The elongation at break and the impact resistance were significantly improved compared with that of neat PLA when the SBS content was above 50 wt%. Moreover, poly(butadiene-b-methyl methacrylate)(PBM) copolymer was also prepared and used as a compatibilizer for PLA/HDPE blend. When the blend weight ratio of PLA to HDPE and PBM was 20:80:3, the elongation and impact resistance were significantly improved compared with those of neat PLA and PLA/HDPE blend. The combination of anionic polymerization and mercaptan/ε-caprolactam living polymerization provided a new method for preparation of block copolymer. Using the new strategy facilitated preparing block copolymers in mild temperatures; thus, it is feasible for use in industrial applications.

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